JPH0711109B2 - Heavy coating agent for fiber flooring - Google Patents

Abstract

Heavy-duty carpet backing materials based on amorphous polyolefins tend to have poor strength; permanent indentation points are formed under high stress. The addition of isotactic polypropylene is effective against this but increases the melt viscosity of the material and reduces the flexibility and the lying characteristics. <??>A (grafted) polyolefin reacted partially or completely with an organic unsaturated acid or with an organic unsaturated anhydride is used; this may be the atactic polyolefin itself or the isotactic polyolefin used in addition to this. Materials of this type are easy to process, withstand high stress and exhibit easy elastic recovery. <??>Textile floor coverings, for example carpet tiles.

Description

DETAILED DESCRIPTION OF THE INVENTION Heavy coating finishing agents (Schwerbeschicht-ungsmasse) for rugs based on amorphous poly-α-olefins (APAO)
Have been known for a long time in addition to those consisting of bitumen, PVC- and polyurethane mixtures. A typical formulation consists of about 30% thermoplastic binder and 70% filler. As binders there are used, for example, different qualities of atactic polypropylene (APP) (forced production in homopolymerization or copolymerization) or limited atactic-co- or terpolymers. Of the last-mentioned group, propene / butene-1 / ethene-terpolymers, propene / ethene-, butene-1 / ethene- and butene-1 / propene-copolymers are particularly good. Has been proven.

Isotactic-polypropylene (IPP), resin, wax or paraffin may be selectively added to intentionally modify its properties. Limestone powder is mainly used as the filler, and barite in some cases.

Heavy coating agents are generally applied as hot melt adhesives to various pretreated rug surface materials that have been coated with a latex- or hot melt-priming agent (eg, H. Koerner, "Die Verwendung von. ataktschem P
olypropylenam Beispiel der Teppichschwerbeschichtu
ng ", Kunststoffe 65 , p. 467 et seq., 1975). A particular area of application of coating agents is rug tiles.

With the increasing use of rugs in homes, hospitals, bank teller halls, etc., the demand for good heavy coating finishes is increasing. Rug tiles (Tippichfliesen) made of atactic-polyolefin are often challenged for defective stiffness. The behavior of tiles lying down under high loads, such as those that occur when walking under the legs of a chair or table or on high heels (Li
egehaltungen) and residual subsidence and harm that affects dimensional stability. The cause lies in the plastic deformation of the coating agent under the influence of load. This phenomenon is "cold flow"
Is called.

This cold flow can be reduced by the addition of IPP or the use of high molecular weight atactic polypropylene. However, this adversely affects the flexibility and thus the lying behavior. Regarding the processing technology, the melt viscosity of the processing agent, which is increased at that time, causes a problem and causes problems. Further, heavy IPP-rich heavy coating finishes tend to shrink due to the post-crystallization process. Therefore, in order to obtain a harmonious picture, in practice efforts are usually made to limit the addition of IPP to the extent just needed.

The object of the present invention is therefore that the customary hot-melt technology can be used for processing and a small penetration depth under load-i.e. A low cold flow-adds a partial elastic recoil capacity. It is in the heavy coating processing agent that I have.

This problem of the present invention is solved by a polyolefin-based heavy coating processing agent containing a filler. The polyolefin is here partially or completely reacted with an organic unsaturated acid or an organic unsaturated acid anhydride.

Particularly advantageous embodiments are given below: A; IPP-a binder commonly used to improve rigidity
The components are exchanged for functionalized predominantly crystalline polyolefins by reacting with a double bond containing organic acid or the corresponding acid anhydride in a suitable manner.

B. In commercially available heavy coating finishes, the components of the atactic polyolefin are exchanged for fully or partially amorphous (low crystalline) polyolefins which are also functional.

Polymers that can be used according to embodiment A include, for example: -Polypropylene grafted with acrylic acid, methacrylic acid or fumaric acid. This group of polymers includes, for example, BP Che
belongs to the POLYBOND-type sold by micals Limited.

-Polypropylene grafted with maleic anhydride (MSA). Corresponding polymers are sold, for example, by Himont under the name HERCOPRIME.

Suitable unsaturated acids are in principle maleic acid, maleic acid monoalkyl esters, fumaric acid monoalkyl esters and aconitic acid. In addition to polypropylene, propylene / ethylene-copolymer, propene / butene-
It is also possible to use 1-copolymers, butene-1 / ethylene-copolymers-as well as mixtures of polypropylene with copolymers mentioned last.

Generally, the above-mentioned graft copolymers of polypropylene are prepared by the customary graft polymerization of unsaturated acids or anhydrides in the presence of a graft substrate and a radical former. Peroxides, azo compounds or energy-rich radiation are used as radical formers. Representative synthetic examples are described in European Patent Application Publication No. 188,926, Belgian Patent No. 692,301, Japanese Patent Publication No. 41-27421 or US Pat. No. 3,499,819.

Polymers functionalized in this way are 1 to 20%, in particular 3 to 12%.
%, Based on binder, added to binder in considerable amount. In order to achieve a sufficient effect, the acid number of the functionalized polymer is> 10 mg (KOH) / g, especially 40-60 mg (KOH) / g (this acid number is It is measured after pre-opening with water). Practically acceptable processing viscosities are obtained when the MFI 230/2 of the graft copolymer is> 30 g / 10 min, in particular 40 g / 10 min.

The polymer of embodiment B is produced, for example, by radically grafting maleic anhydride or fumaric acid onto an amorphous polyolefin. A particularly suitable amorphous polyolefin is the propene / butene / ethylene terpolymer (corresponding to DE 2,930,106) sold by Huels under the trade name VESTOPLAST. Synthesis of this type of graft copolymer proceeds successfully in the solution or in the melt in the presence of peroxide. Corresponding examples are, for example, DE-A-1,546,982, DE-A-20,232, DE-A-2,633.
No. 2,869 and Journal of Applied Polymer Scie
nce, Vol. 13, page 1625 et seq. (1969).

It should be noted that degradation of the trunk polymer can often be observed in the course of radical graft polymerization. Especially when tertiary carbon is present in the polymer chain, such decomposition can be noticeably negative. This is because, according to the present invention, the cold flow and the associated penetration depth after loading increase as the molecular weight decreases. However, the positive effects that can be obtained by the introduction of the carboxyl group far outweigh the negative effects of the peroxide decomposition of the polymer that occurs in parallel with the graft polymerization.

Amorphous polyolefins containing polybutadiene can also be used. It is known from DE-A-2,708,757 to increase the degree of grafting of polybutadiene during the grafting reaction. When such a graft polymerization aid is used, partial crosslinking of the polymer occurs at the same time.
If a raw polymer containing double bonds is used (eg propene / ethene / hexadiene-1,5-terpolymer), the addition of peroxide can be omitted. This is because the graft polymerization proceeds purely thermally by the method of en-Reaktion (see for example DE-A 2,401,149 or US-A 3,862,265). In the case of graft polymerization in the molten state,
The extruder embodiment according to U.S. Pat. No. 3,260,708 is advantageous. However, in some cases it can also be carried out batchwise in a mixing vessel.

Suitable amorphous graft copolymers are 2-40, especially 3-10 mg.
It has an acid value of (KOH) / g (in the case of an acid anhydride, the acid anhydride group is previously reacted with water and the non-covalently bound component is excluded). It has a maleic anhydride content of 0.26
This is the case with .about.0.9% by weight maleic anhydride-graft copolymer.

Some non-covalently bonded monomers present during the grafting reaction (eg maleic anhydride) do not have a negative effect on the mechanical properties of the coating process. However, in order to avoid odor problems, it can be easily reacted with long-chain alcohols or amines to the corresponding half-esters or amides.

The melt viscosity of amorphous graft polymer at 190 ℃ is 300〜60,0
00, especially in the range of 1,000 to 20,000 mPa.s. By varying the proportion of wax, resin or IPP, the desired melt viscosity in the binder can be adjusted. Generally, with a filler content of 70% by weight, the binder content is 19
Good processability heavy coating finishes are obtained when they have a melt viscosity of from 5,000 up to 20,000 mPa.s at 0 ° C.

Besides amorphous graft polymer, 70g / 10min MFI 190/5
Binders with addition of 3-5% isotactic polypropylene having a value of 3 to 5% are particularly advantageous in respecting the highest rigidity of the processing agent without unacceptably degrading the flexibility or processing viscosity. Is known.

Limestone, barite and mica are suitable as fillers. 24-192 μm limestone powder in each case (commercially available products are eg Jura-Weiss from Kalksteinwerks Ulm
Fuellstoff, of type G.Gr/Al) is particularly advantageous. The filler content can vary between 50 and 85% by weight, with 70% being particularly advantageous. The highest filler content is possible with high molecular weight butene-1 high atactic polyolefins.

In the case of a polymer grafted with maleic anhydride, it is not necessary to add water for ring opening of the acid anhydride. That is, the trace amount of moisture present on the filler surface is clearly sufficient for ring opening.

Filler-containing processing agents are generally those which first melt the atactic component (e.g. APAO or MSA-grafted APAO) in a mixer which is under an inert gas atmosphere, and then at a temperature of 200 ° C an isotactic polymer (e.g. Functionalized IPP)
And a uniform mixture. Finally the filler is incorporated after addition of viscosity modifiers such as waxes and resins.

10x10x from heavy coating finish to evaluate mechanical properties
A press-formed plate with a dimension of 0.2 (cm) is produced (melting at 190 ° C. in a mold, pressing time at 150 ° C. for 10 minutes, storage time after production; 48 hours at room temperature). About this plate, round 1 cm ²
The penetration depth of the dumbbells is measured after 4 hours under a load of 50 kp / cm ² (4-hour standing time). Furthermore, the reaction capacity (residual penetration depth) is measured 10 minutes after the load is released. The first measured value is a measure of rigidity, and the second measured value is the elasticity and elastic properties of the processing agent.

In comparing conventional formulations with newly developed preparations, IP
Stiffness improved at least 40% in heavy coatings by replacing P with functional isotactic polymer or APP or APAO with amorphous graft copolymer, ie depth of penetration under load It turns out that it brings about the decrease of. Residual deformation or penetration depth is significantly reduced due to improved recoil.

This is achieved in practice with a relatively small amount of functionalized isotactic polymer, for example, in order to obtain the same stiffness that can be achieved with only high IPP-contents. It means to succeed. In this way the processing viscosity of the processing agent is limited to an acceptable level. Another advantage of the newly developed heavy coating finishing agent is that it provides reduced levels of shrinkage and, due to the high flexibility, an improved level of behaviour, in such a coated rug.

The following substances are used in the examples below: APAO 1: amorphous propene / butene with a melt viscosity of 8,000 mPa.s at 190 ° C. and a penetration of 100/25/5 (according to DIN 52010) of 15 0.1 mm. 1 / Ethene-terpolymer.

APAO2: Amorphous propene / butene-1 / ethene-terpolymer with a melt viscosity of 50,000 mPa.s at 190 ° C and a penetration of 100/25/5 of 20 0.1 mm (according to DIN 52010).

APAO3: Amorphous butene-1 / propene / ethene-terpolymer with a melt viscosity of 8,000 mPa.s at 190 ° C and a penetration of 100/25/5 of 15 0.1 mm (according to DIN 52010).

IPP1: isotactic polypropylene with MFI 190/5 (DIN 53 753, code T) of 70 g / 10 min.

Wax 1: Polyethylene wax with a dropping point of 120 ° C and an average molecular weight of 1,600.

Resin 1: Resin family hydrocarbon resin with a softening point of 100 ° C (ring and ball method) and an average molecular weight of 2,400.

KP-P1: MFI 190/5 with 64 g / 10 min, polypropylene grafted with 6% acrylic acid.

KP-P2: polypropylene with 2% maleic anhydride grafted with a J-value of 70 ml / 10 min.

In each case 0.2 part of IRGANOX B 225 (Ci
ba-Gaigy) is used.

Limestone used as a filler is Jura-Weiss G.Gr.Al.

Comparative Example: Preparation and properties of a commercial heavy coating finishing agent: 95 parts of APAO 1 are placed in an oil-heated vessel under nitrogen atmosphere, mixed with 0.2 part of stabilizer and melted at 200 ° C. Mix 5 parts IPP 1 with stirring.

The resulting binder is mixed with limestone powder in a ratio of 30:70 and the mixture is homogenized. The properties of the resulting binder are listed in Table 1 as Processing Agent A.

Processing agents B and C in Table 1 are likewise commercially available heavy coating processing agents. These are also used for comparison with the processing agent of the present invention described later.

Example 1 Preparation and Properties of Acrylic Acid Grafted Polypropylene Modified Heavy Coating Finishing Agent: 95 parts of APAO 2 are placed in a nitrogen atmosphere in an oil heated mixing vessel and mixed with 0.2 parts of stabilizer. Then, it is melted at 200 ° C. 5 parts of KP-P 1 are admixed with stirring and the resulting binder is mixed with limestone powder in a ratio of 30:70. The mixture is homogenized. The properties of the heavy coating processing agent are listed in Table 2 as processing agent D.

Example 2: The same as Example 1. However, in the case of this embodiment
Replace KP-P 1 with the same amount of KP-P 2. The properties of the heavy coating processing agent are listed in Table 2 as processing agent E.

Example 3: Replacing IPP with the same amount of KP P 1 in a commercially available heavy coating finish C (see Table 1). The properties of the processing agent F thus obtained are summarized in Table 2.

Example 4: 450 g of APAO1, 11.25 g of maleic anhydride and 1.35 g of dicumyl peroxide were carefully mixed in a kneader to produce an amorphous (or low crystalline) MSA-graft copolymer. Then place in a nitrogen atmosphere and warm to 180 ° C. at a heating rate of 2 ° C./min. The processing agent is left at this temperature for a further 30 minutes with continuous kneading and then processed directly into the heavy-coated processing agent. The graft copolymer thus produced had an acid value of 5.9 mg (KOH) / g (measured after reacting with water and twice purified by precipitation with isopropanol) and 5,000 at 190 ° C.
Melt viscosity of mPa.s, softening point of 104 ° C (DIN 52 011) and
It has a penetration of 15 0.1 mm (DIN 52 010).

95 parts of graft copolymer, 5 parts of IPP 1 and 0.2 parts of stabilizer are placed in a mixing vessel under a nitrogen atmosphere with stirring.
Melt at 200 ° C. Limestone powder is added to the resulting binder in a ratio of 30:70 and the mixture is homogenized. The properties of the heavy coating processing agent are listed in Table 3 as processing agent G.

Example 5 450 g of APAO 2 under the same conditions as described in Example 4
Graft MSA to. The amorphous graft polymer obtained has an acid value of 4.2 mg (KOH / g), a melt viscosity of 190,000 mPa.s at 190 ° C., a softening point of 107 ° C. and a penetration degree of 140.1 mm. All characteristic data are also shown in Table 4.

Perform as in Example 4. A heavy coating finishing agent having the properties described in Table 3 is obtained.

Example 6 450 g of APAO 2 under the same conditions as described in Example 4
Is grafted with 22.5 g MSA in the presence of 2.7 g dicumyl peroxide. The obtained amorphous graft polymer is
It has an acid value of 8.8 mg (KOH) / g, a melt viscosity of 190,000 mPa.s at 190 ° C, a softening point of 160 ° C and a penetration of 100.1 mm. All characteristic data are also shown in Table 4.

The same procedure as in Example 4 is carried out to obtain Heavy Coating Processing Agent I (Table 3).

The present invention relates to a heavy coating processing agent for overlying fibrous materials described in the claims, and includes the following as embodiments.

1) A thermoplastic binder is exclusively an atactic polyolefin or a low crystalline olefin copolymer and a small amount of isotactic-polyolefin partially or completely reacted with an acid or an anhydride. The processing agent according to claim 1, wherein the processing agent is contained.

2) Isotactic-reacted with acid or acid anhydride
Polyolefin has an acid value of> 10 mg (KOH) / g and> 30 g / 1
A processing agent according to claim 1 having a 0 minute MFI 230/2.

3) The processing agent according to claim 1, wherein the thermoplastic binder contains an atactic-polyolefin or olefin copolymer partially or completely reacted with an acid or an acid anhydride.

4) The atactic-polyolefin or olefin copolymer partially or completely reacted with an acid or an acid anhydride has an acid value of 3 to 10 mg (KOH) / g and 300 / 60,000 at 190 ° C.
The processing agent according to the above item 2, which has a melt viscosity of mPa.s.

5) The processing agent according to any one of claims 1 and 1 to 4, wherein the binder contains wax, resin, paraffin and / or stabilizer.

6) The processing agent according to any one of claims 1 and 1 to 5, wherein the filler is powdered limestone or barite and is contained in a proportion of 50 to 85% by weight.

Continuation of the front page (72) Inventor Matias Schiurainzel, Federal Republic of Germany, Dorsten 1, Lim Welt, 39 (56) References Japanese Patent Publication No. 54-36720 (JP, B2) Japanese Patent Publication No. 62-9022 (JP, B2) )

Claims (1)

[Claims] 1. A thermoplastic binder based on polyolefin is provided, provided that said polyolefin is based on
Amorphous poly-α-olefin-containing filler-containing heavy coating finishing agent for fiber floorboards, wherein the base polyolefin is partially or completely combined with an organic unsaturated acid or an organic unsaturated acid anhydride. The above-mentioned heavy coating processing agent, which is obtained by reacting with.